Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles

ABSTRACT

Brominated styrenic polymer is recovered from solution in a vaporizable solvent by converting the solution in a devolatilization extruder into a brominated styrenic polymer melt or flow and a separate vapor phase comprised predominately of vaporizable solvent, recovering the melt or flow from the devolatilization extruder, and allowing or causing the melt or flow to solidify. The solidified brominated styrenic polymer can be subdivided into a powder or pelletized form. Pellets so made have improved hardness and/or crush strength properties along with reduced formation of fines. Brominated anionic styrenic polymer is preferably used in the process.

REFERENCE TO RELATED APPLICATIONS

This application is the National Stage of International Patent Appl. No.PCT/US2007/073805 filed on Jul. 18, 2007, which in turn claims thebenefit of U.S. Provisional Patent Appl. Nos. 60/832,184, filed on Jul.20, 2006, and 60/867,548, filed on Nov. 28, 2006, the disclosures ofwhich are incorporated herein by reference.

BACKGROUND

U.S. Pat. Nos. 5,677,390, 5,686,538, 5,767,203, 5,852,131, 5,852,132,5,916,978, 6,113,381, 6,207,765, 6,232,393, 6,232,408, 6,235,831,6,235,844, 6,326,439, and 6,521,714 describe very desirable processtechnology for producing brominated styrenic polymers such as brominatedpolystyrene having the best known properties of any previously-knownbrominated styrenic polymer. In this connection, the terms “brominatedstyrenic polymer” and “brominated polystyrene” as used in thespecification and in the claims hereof refer to a brominated polymerproduced by bromination of a pre-existing styrenic polymer such aspolystyrene or a copolymer of styrene and at least one other vinylaromatic monomer, as distinguished from an oligomer or polymer producedby oligomerization or polymerization of one or more brominated styrenicmonomers, the properties of the latter oligomers or polymers typicallybeing considerably different from brominated polystyrene in a number ofrespects. Also as used herein, including the claims, the term “anionicstyrenic polymer” or “anionic polystyrene”, terms commonly used bypersons skilled in the art, denotes that the polymer referred to hasbeen produced by use of an anionic polymerization initiator, such as alithium alkyl. The terms “brominated styrenic polymer” and “brominatedpolystyrene” include and are generic to the terms “brominated anionicstyrenic polymer” or “brominated anionic polystyrene”. These genericterms also include, for example, brominated styrenic polymers producedby bromination of styrenic polymers or polystyrene made by free radicalpolymerization.

As indicated in the above patents, the common method for recovering thebrominated styrenic polymer from the liquid phase of the brominationreaction mixture involves deactivating the catalyst with an aqueousquenching medium, separating the brominated polymer-containing organicphase from the aqueous phase, stripping the organic phase of its solventusually by feeding the organic phase into boiling water whereby thebrominated polymer is precipitated, recovering the precipitatedbrominated polymer by a liquid-solids separation technique such asfiltration or centrifugation, and drying the resultant finely-dividedbrominated styrenic polymer. It would be highly advantageous if a waycould be found for recovering the brominated styrenic polymer in a moreefficient and less costly manner.

When blending a brominated styrenic polymer with a substratethermoplastic polymer to be flame retarded, it is desirable that thebrominated styrenic polymer be in the form of pellets, granules, orpastilles. Unfortunately, a characteristic of brominated anionicstyrenic polymers such as brominated anionic polystyrene, and to alesser extent, brominated styrenic polymer made by free-radicalpolymerization as well, is a propensity to form substantial amounts ofsmall particles and powders when attempts are made to pelletize theproduct. It appears that the pellets, unless bound together by anextraneous binding agent or the like, tend during formation, handling,and/or packaging to break apart and to revert to small particles andfinely-divided powder, typically referred to as “fines”. Because of thischaracteristic, various conventional pelletizing or compactingprocedures are unsuitable for producing brominated anionic styrenicpolymers essentially free of fines and that during shipment and handlingremain essentially free of fines. As can be readily appreciated, theexistence or formation of fines in a product of this type is not onlydetrimental to the appearance of the pelletized product but in additionis undesired by the consumer.

In order to effectively use brominated styrenic polymers, especiallybrominated anionic styrenic polymers, as flame retardants in certainthermoplastic polymers, the use of binding agents or other extraneousmaterials to maintain the integrity of the flame retardant in pelletizedform, is also deemed undesirable by some consumers. Thus, it isdesirable to be able to produce unadulterated pelletized brominatedstyrenic polymers, especially brominated anionic styrenic polymers, thatdo not form undesirable amounts of fines during their preparation,packaging, shipment, and handling.

In the production of pelletized brominated styrenic polymers, especiallybrominated anionic styrenic polymers, it is important to improve theefficiency of the operation and to minimize operating costs. Recoveryand recycle of fines avoids waste of product and minimizes wastedisposal considerations. However the greater the amount of finesproduced, recovered and recycled, the lower the production rate ofpellets per quantity of polymer being subjected to pelletization. Itwould be highly advantageous, therefore, if a way could be found ofpreparing brominated styrenic polymers, especially unadulteratedbrominated anionic styrenic polymers, in pelletized form in a highlycost-efficient manner while avoiding formation of excessive amounts offines, so that the production rate of high quality pellets is notmaterially impaired. In the case of brominated anionic styrenicpolymers, it would be especially desirable if a way could be found ofproducing granules or pastilles of the polymers. This would enable theachievement of a number of important advantages in the process,including the overall process, the handling and storage of the product,and in the transportation of the product to, and the use of the productby, the end user.

SUMMARY OF THE INVENTION

Pursuant to one group of embodiments of this invention brominatedstyrenic polymers, and especially brominated anionic styrenic polymers,can be recovered much more readily and efficiently, and at lower cost,from solution in a solvent, and especially from solution in the solventin which they were formed, as compared to the common method for recoveryreferred to above.

Pursuant to another group of embodiments of this invention brominatedstyrenic polymers, especially brominated anionic styrenic polymers, cannow be produced and packaged in unadulterated pelletized formessentially free of fines. As used herein, including the claims, theterms “pellets”, “pelletized”, “pelletizing”, etc., refers to a quantityof particles which, if screened using conventional screening practices,are in the size range of that can pass through a screen of about 4standard U.S. mesh size and which are retained on a screen of about 40standard U.S. mesh size. The particles in such size range can be of anyshape and thus may also be referred to as granules, and thus as usedherein including the claims the terms “pellets” “pelletized”,“pelletizing”, etc. include respectively “granules”, “granular”,“granulating”, etc. Due to electrostatic charges, incomplete screening,or the like, some small amount (e.g., less than about 5 wt % based onthe total weight of the pellets in such size range) of finer-sizedparticles may remain in the product. By the term “unadulterated” as usedherein including the claims is meant that no extraneous ingredients suchas binders (e.g., waxes or other polymeric or oligomeric substances),inorganic salts, or the like are added to the brominated styrenicpolymer prior to or during the preparation the pellets. Instead, thebrominated styrenic polymer contains only residual impurities thatremain in the brominated polymer after its preparation.

Moreover, preferred embodiments of this invention make possible on aneconomical basis the benefits of avoiding formation of undesirableamounts of fines, since only relatively small amounts of fines areproduced in the operation and the unadulterated pellets formed have goodhardness and crush strength. In fact, in preferred processes of thisinvention small amounts of dry fines that may exist in the product beingformed can be recovered and recycled in the operation without muchexpense or difficulty.

Other particularly preferred embodiments of this invention enable theproduction of brominated anionic styrenic polymers in the form ofgranules or pastilles which have relatively smooth surfaces and whichthus are more readily handled, stored, shipped, and used withoutformation of undesirable amounts of fines.

In each of the embodiments of this invention a “polymer melt”, “polymerflow”, “melt”, or “flow” is formed from a brominated styrenic polymer,preferably a brominated anionic styrenic polymer, in a devolatilizationextruder, As used herein including the claims, the terms “polymer melt”,“polymer flow”, “melt”, or “flow” refer to the fact that the brominatedstyrenic polymer within the devolatilization extruder becomes a meltedmass and/or a sufficiently softened mass that will thenceforth proceed(i.e., flow) through the remainder of the devolatilization extruder(including any extension that may be added thereto) and a die disposedat the discharge end of the machine under the thrust provided within themachine by the screw(s) thereof. It matters not whether, strictlyspeaking, a true melt of brominated styrenic polymer has been formed orwhether the brominated styrenic polymer has merely been softened to suchan extent that it will flow as just indicated.

Accordingly, among one group of embodiments of this invention there areprovided processes for recovering brominated styrenic polymer, typicallyhaving a bromine content of at least about 50 wt %, from solution in avaporizable solvent, preferably a vaporizable halogenated solvent. Theseprocesses comprise converting in a devolatilization extruder anadmixture of extrudable viscosity comprised of brominated styrenicpolymer and a vaporizable organic solvent into a brominated styrenicpolymer melt or flow and a separate vapor phase comprised predominatelyof vaporizable solvent, recovering said melt or flow of brominatedstyrenic polymer while in the form of a melt or flow from thedevolatilization extruder, and allowing or causing said melt or flow tosolidify. In preferred embodiments of this group, the process preferablyfurther comprises subdividing the solidified melt into a powder,granular or pelletized form. Alternatively or in addition, the processfurther comprises recovering and allowing or causing the vapor phase toliquefy as vaporizable solvent. Preferably, such liquefied solvent isrecycled as vaporizable solvent used in forming additional solution ofbrominated styrenic polymer. In particularly preferred embodiments ofthis group of embodiments an admixture of brominated styrenic polymerand vaporizable organic solvent of less than extrudable viscosity isconverted into an admixture of extrudable viscosity which issubsequently processed in a devolatilization extruder as describedearlier in this paragraph. This conversion from less than extrudableviscosity to extrudable viscosity is typically accomplished by removing,e.g., by distillation or flash distillation, a sufficient amount ofvaporizable organic solvent, preferably a vaporizable halogenatedorganic solvent, from the admixture of less than extrudable viscosity toform an admixture of extrudable viscosity. In especially preferredembodiments of this group of embodiments, the admixture of less thanextrudable viscosity is formed by brominating styrenic polymer invaporizable organic solvent, preferably a halogenated organic solvent,and obtaining from the bromination process an admixture of less thanextrudable viscosity comprised of brominated styrenic polymer, typicallyhaving a bromine content of at least about 50 wt %, and vaporizablesolvent, preferably a halogenated organic solvent. Often such admixturesof less than extrudable viscosity are solutions of brominated styrenicpolymer having a bromine content of at least 50 wt %, preferably atleast about 60 wt %, and more preferably at least about 67 wt %, in avaporizable organic solvent, preferably a vaporizable halogenatedorganic solvent. In some embodiments of this group of embodiments,particular ways of conducting the bromination reaction and/or ensuingwork up operations leading to the formation of an admixture of less thanextrudable viscosity are utilized as preliminary operations. In some ofthe embodiments of this group of embodiments, before processing anadmixture of brominated styrenic polymer and vaporizable organic solventof extrudable viscosity in a devolatilzation extruder as describedearlier in this paragraph this admixture is subjected to a coalescingfiltration to remove entrained water and dissolved salts that may bepresent in such admixture. Another preferred operation that may beperformed in the various embodiments of this group of embodiments ispreheating of the admixture of extrudable viscosity if it is in the formof solids at a temperature below about 175° C. prior to being atextrudable viscosity for processing within the devolatilization extruderas described earlier in this paragraph. This preheating can beaccomplished either in a preheater section already associated with thedevolatilization extruder as manufactured or by use of a separatepreheater which discharges its suitably preheated contents into theinlet portion of the devolatilization extruder. The preheating shouldraise the temperature of the admixture so that it can be fed in at leasta softened movable state, a partially liquefied state, a liquefiedstate, or at an extrudable viscosity into the devolatilization extruder.In addition, temperature control within the extruder can be effected byscrew design, screw speed, and/or barrel temperature regulation. Also,the devolatilization extruder may be provided with cooling capabilitiesto avoid localized overheating.

Among another group of embodiments of this invention there are providedprocesses for preparing pelletized brominated styrenic polymer,typically having a bromine content of at least about 50 wt %, from theextrudate from a devolatilization extruder functioning as described inthe immediately preceding paragraph. The various embodiments of thisgroup of embodiments utilize any of the embodiments described in theimmediately preceding paragraph involving the processing of an admixtureof extrudable viscosity in a devolatilization extruder, including eachof the various embodiments described in the immediately precedingparagraph that involve one or more operations conducted prior to suchprocessing in the devolatilization extruder. Thus instead of recoveringa melt or flow of brominated styrenic polymer while in the form of amelt or flow from the devolatilization extruder, and allowing or causingsaid melt or flow to solidify, in this group of embodiments the melt orflow from the devolatilization extruder is passed through a die toproduce one, or more than one, emerging strand of brominated styrenicpolymer melt or flow, the strand(s) is/are allowed or caused tosolidify, and the strand(s) is/are subdivided into solidified pellets ofbrominated styrenic polymer. Preferred ways of processing such strand(s)form additional embodiments of this group of embodiments of thisinvention.

Still another group of embodiments of this invention involve a processof producing granules or pastilles of unadulterated brominated anionicstyrenic polymer, which process comprises:

-   -   converting in a devolatilization extruder, an admixture of        brominated styrenic polymer and a vaporizable organic solvent        into a melt or flow of brominated anionic styrenic polymer and a        separate vapor phase of said solvent; and    -   forming from said melt or flow a downwardly oriented plug flow        from at least one orifice in a manifold or nozzle that is in        proximity to a cooled traveling planar member, said planar        member being impervious to cooling liquid and having an upper        and lower surface, whereby there is a gap between the lower        portion of the orifice and said upper surface, so that at least        a portion of a plug of molten unadulterated brominated anionic        styrenic polymer either (i) bridges said gap and forms a        separate individual granule or pastille on the upper surface of        said planar member, or (ii) freely drops from the lower portion        of the orifice and falls upon the upper surface of said planar        member and forms an individual granule or pastille on the upper        surface of said planar member, said traveling member being        cooled by a mist or spray of cooling liquid contacting the lower        surface of said planar member.

The above and other embodiments, features and/or advantages of thisinvention will become still further apparent from the ensuingdescription, accompanying drawings, and appended claims.

Except for the embodiments involving preparation of granules orpastilles from brominated anionic styrenic polymer such as brominatedanionic polystyrene, in all of the other embodiments of this inventionsuch as those referred to above and those described hereinafter,preferred brominated styrenic polymers are those formed by brominationof styrenic polymers formed by free radical polymerization(“free-radical styrenic polymers”). Especially preferred are brominatedstyrenic polymers formed by bromination of styrenic polymers prepared byanionic polymerization (“anionic styrenic polymers”). Of thefree-radical styrenic polymers, rubber-free polystyrene formed by freeradical polymerization is preferred (“free-radical polystyrene”). Of theanionic styrenic polymers, rubber-free polystyrene formed by anionicpolymerization is preferred (“anionic polystyrene”). While other typesof brominated styrenic polymers such as brominated styrenic polymerformed by bromination of styrenic polymer formed by cationicpolymerization can be used they are not preferred.

As used herein, including the claims, the term “extrudable viscosity”means that the admixture has a viscosity in the range of about 5000 toabout 5,000,000 centipoise at 100 reciprocal seconds while at atemperature in the range of about 175° C. to about 300° C. Suchadmixtures can be caused to flow (e.g. by means of a suitable pump) intoand through a devolatilization extruder and be worked within theextruder to release vaporizable organic solvent in the vapor state whenthe admixture is at least at one or more temperatures in and/or abovethe foregoing range. By the term “admixture” is meant a mixture ofspecified components, which mixture can be in the form of solids, orpreferably in the form of at least one liquid phase and which, whetherin the form of one liquid phase or more than one liquid phase, can haveone or more solid phases suspended therein. It should be noted that theterm “extrudable viscosity” refers to a viscosity that the admixturewill achieve when it is being processed within the devolatilizationextruder. Prior to this processing the admixture of extrudable viscosityneed not be, and usually is not, at extrudable viscosity.

In all process embodiments of this invention the admixture of extrudableviscosity preferably is not exclusively in the form of solids, butrather is in the form of a viscous flowable mass having a liquid phasewhich can have solids suspended or dispersed therein.

All references in this specification or in the ensuing claims to“pressure” in connection with a devolatilization extruder or its userelate to the reduced pressures (vacuum) imposed upon the melt or flow,and do not relate to the force exerted upon the melt or flow by thescrew(s) of the devolatilization extruder. To determine in anyembodiment of this invention the amount of organic solvent in thepolymer, it is desirable to use NMR analysis. The result should showthat the melt or flow of brominated styrenic polymer that has exitedfrom the outlet portion of the devolatilization extruder contains anaverage of less than about 10,000 ppm (wt/wt), and preferably less thanabout 5000 ppm (wt/wt), and still more preferably less than about 1000ppm (wt/wt) of the organic solvent in steady state operation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram illustrating an overall process for thepreparation and isolation of the pelletized unadulterated brominatedstyrenic polymers of this invention.

FIG. 2 is a schematic top view of a mechanical system suitable forproducing pursuant to the processes of this invention, pelletizedunadulterated brominated styrenic polymers and preferably, pelletizedunadulterated brominated anionic styrenic polymers, of this invention.

FIG. 3 is a schematic side view of the system of FIG. 2.

FIG. 4 is a block diagram illustrating an overall process of thisinvention for the preparation of granules or pastilles of unadulteratedbrominated styrenic polymers.

FURTHER DETAILED DESCRIPTION OF THE INVENTION Some Embodiments InvolvingRecovering Brominated Styrenic Polymer

A) A process for recovering brominated styrenic polymer from admixturein a vaporizable organic solvent, which process comprises processing anadmixture of at least extrudable viscosity comprised of brominatedstyrenic polymer typically having a bromine content of at least about 50wt %, preferably at least about 60 wt %, and more preferably at leastabout 67 wt %, and a vaporizable organic solvent, in a devolatilizationextruder to form a melt or flow of such brominated styrenic polymer anda vapor phase comprised of vaporizable organic solvent, recovering fromthe devolatilization extruder such melt or flow of brominated styrenicpolymer while in the form of a melt or flow, and allowing or causingsaid melt or flow to solidify. Preferably, the melt or flow of suchbrominated styrenic polymer that has exited from the outlet portion ofthe devolatilization extruder contains an average of less than about10,000 ppm (wt/wt), more preferably less than about 5000 ppm (wt/wt),and still more preferably less than about 1000 ppm (wt/wt) of theorganic solvent in steady-state operation of the devolatilizationextruder. Preferably, the vapor phase is also recovered.

B) A process for recovering brominated styrenic polymer from admixturein a vaporizable organic solvent, which process comprises

-   -   continuously introducing into the inlet portion of an operating        devolatilization extruder, an admixture of extrudable viscosity,        said admixture comprising brominated styrenic polymer typically        having a bromine content of at least about 50 wt %, preferably        at least about 60 wt %, and more preferably at least about 67 wt        %, and a vaporizable organic solvent, said extruder having an        inlet portion and a polymer melt or polymer flow outlet portion        and at least two sections that can be operated (a) at        temperatures that differ from each other, and (b) under        pressures that differ from each other, one of the at least two        sections being disposed upstream from the other of the at least        two sections, the devolatilization extruder having vapor        collecting apparatus adapted to collect volatiles formed in        these at least two sections; and    -   operating said section disposed downstream at higher temperature        and lower pressure conditions than the temperature and pressure        conditions of said section disposed upstream, so that (a) a flow        or melt of said polymer is formed within the devolatilization        extruder and released from the polymer melt or polymer flow        outlet, and (b) volatiles composed predominately of the solvent        released from the polymer in said at least two sections can be        collected by said vapor collecting apparatus, the melt or flow        of such brominated styrenic polymer that has exited from the        outlet portion of the devolatilization extruder containing an        average of less than about 10,000 ppm (wt/wt), preferably less        than about 5000 ppm (wt/wt), and still more preferably less than        about 1000 ppm (wt/wt) of the organic solvent in steady-state        operation of the devolatilization extruder.

C) A process for recovering brominated styrenic polymer from admixturewith a vaporizable solvent, preferably a vaporizable halogenatedsolvent, which admixture is an admixture of less than extrudableviscosity, such as a solution containing in the range of about 15 toabout 40 wt % of brominated anionic styrenic polymer (preferablybrominated anionic polystyrene) formed by brominating to a brominecontent of about 50 wt %, preferably at least about 60 wt %, and morepreferably at least about 67 wt %, and anionic styrenic polymer,preferably anionic polystyrene, having a GPC weight average molecularweight in the range of about 2000 to about 200,000, preferably in therange of about 2000 to about 10,000, and more preferably in the range ofabout 3000 to about 7000, such process comprising:

-   -   concentrating or converting such admixture into an admixture of        extrudable viscosity by distillation, preferably by flash        distillation; and    -   utilizing such admixture of extrudable viscosity as the feed in        the process as described in embodiment A) or embodiment B)        above.

In embodiments of this invention involving concentrating or converting aprecursor admixture, e.g., a solution or suspension, of less thanextrudable viscosity by utilizing distillation or flash distillation toaccomplish concentration or conversion to an admixture of extrudableviscosity, several advantages are achieved. In addition to introducinginto a devolatilization extruder a more concentrated admixture orsolution for conversion into a melt or polymer flow and thus reducingthe amount of solvent to be recovered by operation of thedevolatilization extruder, the initial solution of the brominatedstyrenic polymer is heated to effect the distillation or flashdistillation. Thus by promptly feeding the distilled or flash distilledadmixture of extrudable viscosity into the devolatilization extruder,such admixture is in effect preheated, thus reducing the total heatenergy required by the devolatilization extruder to convert theadmixture into a melt or polymer flow. Concentration also removes waterwith the distilled solvent so that any organic solvent removed in thedevolatilization extruder is anhydrous and suitable for direct recycleto bromination without a separate drying step. In addition, theanhydrous feed to the devolatilization extruder is less corrosivebecause of the absence of water in such feed. In embodiments whereconcentrating the brominated styrenic polymer admixture is not required,the same advantages (except for the removal of water) can be achieved bypreheating the admixture of extrudable viscosity prior to feeding it tothe devolatilization extruder.

Also, unlike the recovery process of U.S. Pat. No. 5,043,421, whichrequires use in an extruder of at least one non-solvent such as analkanol or ketone (specifically methanol, 2-propanol, or acetone), therecovery embodiments of this invention do not require use of any suchnon-solvent. In other words, the recovery processes of this inventionpreferably do not feed into the devolatilization extruder any suchnon-solvent, and preferably the recovered extrudate is devoid ofdetectable amounts of such alcoholic or ketonic non-solvents.

Some Embodiments Involving Forming Pelletized Brominated StyrenicPolymer

1) A process for producing pelletized brominated styrenic polymer fromadmixture in a vaporizable organic solvent, which process comprisesprocessing an admixture of at least extrudable viscosity comprised ofbrominated styrenic polymer typically having a bromine content of atleast about 50 wt %, preferably at least about 60 wt %, and morepreferably at least about 67 wt %, and a vaporizable organic solvent, ina devolatilization extruder to form a melt or flow of such brominatedstyrenic polymer and a vapor phase comprised of vaporizable organicsolvent, recovering from the devolatilization extruder such melt or flowof brominated styrenic polymer while in the form of a melt or flow, andconverting such melt or flow into solid pellets of brominated styrenicpolymer.

2) A process for producing pelletized brominated styrenic polymer fromsolution in a vaporizable solvent, which process comprises converting ina devolatilization extruder an admixture of brominated styrenic polymertypically having a bromine content of at least about 50 wt %, preferablyat least about 60 wt %, and more preferably at least about 67 wt %, anda vaporizable organic solvent into a brominated styrenic polymer melt orflow and a separate vapor phase comprised predominately of vaporizableorganic solvent, allowing or causing said melt or flow of brominatedstyrenic polymer while in the form of a melt or flow to pass from thedevolatilization extruder through a die thereby producing emergingstrands of brominated styrenic polymer melt or flow, allowing or causingsaid strands to solidify, and subdividing the strands into solidifiedpellets of brominated styrenic polymer.

3) A process for producing pelletized brominated styrenic polymers froma solution in a vaporizable solvent, which process comprises:

-   -   converting in a devolatilization extruder, an admixture of        brominated styrenic polymer, preferably an admixture of        brominated anionic styrenic polymer, and a vaporizable organic        solvent into a melt or flow of brominated styrenic polymer,        preferably a melt or flow of brominated anionic styrenic        polymer, and a separate vapor phase of said solvent;    -   extruding the melt or polymer flow from the devolatilization        extruder through a die to produce traveling strand(s) of        extruded polymer melt or polymer flow;    -   enabling and/or causing such traveling strand(s) to solidify and        be broken, subdivided, or otherwise converted into pellets of        the brominated styrenic polymer; and    -   subjecting the pellets to size classification to remove and        recover from such product (a) oversized particles, if any,        and (b) fines, if any, that may be present in such product.        The first mentioned step of this embodiment, that of converting        a solution of brominated styrenic polymer into a melt or polymer        flow of brominated styrenic polymer in a devolatilization        extruder, can be, and preferably is, conducted as in the        above-described product recovery embodiments. Also by preheating        the solution or concentrating the solution by use of flash        distillation before feeding the more concentrated solution to        the devolatilization extruder, the above-described advantages of        reducing the amount of solvent to be removed by, and reducing        the heat energy requirements of the devolatilization extruder to        produce the polymer melt or polymer flow, can be achieved.

Apart from the advantages afforded by pre-concentrating and/orpreheating the brominated styrenic polymer solution, an advantage of theforegoing pelletizing embodiment of this invention is the fact that itis possible to use unadulterated brominated styrenic polymers, such asunadulterated brominated anionic styrenic polymers, and thereby formpellets of unadulterated brominated styrenic polymers, such asunadulterated brominated anionic styrenic polymers which have desirableproperties such as improved hardness and reduced fines-producingtendencies during manufacture, handling, storage, and use.

4) A process for the preparation of a brominated styrenic polymer inpelletized form, which process comprises:

-   -   brominating a styrenic polymer under superatmospheric pressure        in a vaporizable organic solvent and in the presence of a Lewis        acid bromination catalyst, and in a closed reaction system in        which substantially all of the hydrogen halide coproduct is        retained in the reaction mixture;    -   quenching the catalyst to thereby form (i) an organic phase        containing dissolved brominated styrenic polymer and (ii) an        aqueous phase containing hydrogen halide;    -   separating phases (i) and (ii) from each other, and if phase (i)        has a viscosity less than extrudable viscosity, concentrating        organic phase of (i) to form an admixture of extrudable        viscosity;    -   continuously introducing organic phase of (i) or admixture of        extrudable viscosity into the liquids inlet portion of an        operating devolatilization extruder having a liquids inlet        portion and a polymer melt or polymer flow outlet portion and at        least two sections that can be operated (a) at temperatures that        differ from each other, and (b) under pressures that differ from        each other, one of the at least two sections being disposed        upstream from the other of the at least two sections, the        devolatilization extruder having vapor collecting apparatus        adapted to collect volatiles formed in these at least two        sections; and    -   operating said section disposed downstream at higher temperature        and lower pressure conditions than the temperature and pressure        conditions of said section disposed upstream, so that (a) a        flowable polymer melt or polymer flow of said polymer is formed        within the devolatilization extruder and can leave from the at        least one polymer melt or polymer flow outlet, and (b) volatiles        composed predominately of the solvent released from the polymer        in said at least two sections are collected by said vapor        collecting apparatus;    -   having said polymer melt or polymer flow leaving the        devolatilization extruder pass through a die to produce one or        more traveling continuous strands of extruded polymer melt or        polymer flow;    -   enabling and/or causing such continuous traveling strand(s) to        solidify and be broken, subdivided, or otherwise converted into        pellets of the brominated styrenic polymer.        Some Further Embodiments of this Invention for Producing        Pelletized Products

Still other embodiments of this invention relate to:

-   -   new pelletized unadulterated brominated styrenic polymers and        preferably, new unadulterated pelletized brominated anionic        styrenic polymers, having superior hardness and/or crush        strength properties;    -   novel continuous processes for the production of highly pure        melts or flows of brominated anionic styrenic polymer        (especially brominated anionic polystyrene) using as raw        materials (1) anionic styrenic polymer (especially anionic        polystyrene), (2) brominating agent (especially bromine), (3)        Lewis acid catalyst (especially aluminum halide catalyst in        which the halogen atoms are bromine and or chlorine, and (4)        vaporizable organic solvent (especially vaporizable halogenated        solvent);    -   novel continuous processes for the production of highly pure        pellets of brominated anionic styrenic polymer (especially        brominated anionic polystyrene), using as raw materials (1)        anionic styrenic polymer (especially anionic polystyrene), (2)        brominating agent (especially bromine), (3) Lewis acid catalyst        (especially aluminum halide catalyst in which the halogen atoms        are bromine and or chlorine, and (4) vaporizable organic solvent        (especially vaporizable halogenated solvent);    -   new pelletized brominated anionic styrenic polymers (especially,        new unadulterated pelletized brominated anionic styrenic        polymers), having reduced levels of ionic bromine (i.e.,        bromide) content, as well as superior hardness and/or crush        strength properties.

In the various embodiments of this invention the extrudate from thedevolatilization extruder typically has an average of less than about10,000 ppm (wt/wt), and preferably less than about 5 000 ppm (wt/wt),and still more preferably less than about 1000 ppm (wt/wt) ppm of theorganic solvent in steady-state operation and thus has desirablehardness and strength properties with attendant reduced fines-formingtendencies.

Some Embodiments Involving Forming Granules or Pastilles of BrominatedStyrenic Polymer

These embodiments comprise a process of producing granules or pastillesof unadulterated brominated anionic styrenic polymer, which processcomprises:

-   -   converting in a devolatilization extruder, an admixture of        brominated styrenic polymer and a vaporizable organic solvent        into a melt or flow of brominated anionic styrenic polymer and a        separate vapor phase of said solvent; and    -   forming from said melt or flow a downwardly oriented plug flow        from at least one orifice in a manifold or nozzle that is in        proximity to a cooled traveling planar member, said planar        member being impervious to cooling liquid and having an upper        and lower surface, whereby there is a gap between the lower        portion of the orifice and said upper surface, so that at least        a portion of a plug of molten unadulterated brominated anionic        styrenic polymer either (i) bridges said gap and forms a        separate individual granule or pastille on the upper surface of        said planar member, or (ii) freely drops from the lower portion        of the orifice and falls upon the upper surface of said planar        member and forms an individual granule or pastille on the upper        surface of said planar member, said traveling member being        cooled by a mist or spray of cooling liquid contacting the lower        surface of said planar member.

In this process, the traveling planar member is preferably an endlessbelt impervious to cooling liquid such as an endless steel belt. In theoperation at least a portion of the plug of molten unadulteratedbrominated anionic styrenic polymer bridges said gap and forms aseparate individual granule or pastille on the upper surface of saidplanar member, or at least a portion of such plug of moltenunadulterated brominated anionic styrenic polymer freely drops from thelower portion of the orifice and falls upon the upper surface of theplanar member and forms an individual granule or pastille on the uppersurface of the planar member. It is also possible to operate such that(a) at least a portion of said plug of molten unadulterated brominatedanionic styrenic polymer bridges said gap and forms a separateindividual granule or pastille on the upper surface of said planarmember; or wherein (b) at least a portion of said plug of moltenunadulterated brominated anionic styrenic polymer freely drops from thelower portion of the orifice and falls upon the upper surface of saidplanar member and forms an individual granule or pastille on the uppersurface of said planar member; (a) and (b) occurring in an alternatingor random manner.

Although other cooling liquids can be employed, said mist or spray ofcooling liquid is preferably a mist or spray of cooling water. The mistor spray is preferably applied to the lower surface of said planarmember below the region in which the separate individual granule orpastille is formed on the upper surface of said planar member.

Another embodiment of this invention is an overall process for producingbrominated anionic styrenic polymer in the form of granules or pastillesof unadulterated brominated anionic styrenic polymer. Such processcomprises:

-   -   brominating an anionic styrenic polymer under superatmospheric        pressure in a vaporizable solvent and in the presence of a Lewis        acid bromination catalyst, and in a closed reaction system in        which substantially all of the hydrogen halide coproduct is        retained in the reaction mixture;    -   quenching the catalyst to thereby form (i) an organic phase        containing dissolved brominated styrenic polymer and (ii) an        aqueous phase containing hydrogen halide;    -   separating phases (i) and (ii) from each other, and if phase (i)        has a viscosity less than extrudable viscosity, concentrating        organic phase of (i) to form an admixture of extrudable        viscosity;    -   continuously introducing organic phase of (i) or admixture of        extrudable viscosity into the liquids inlet portion of an        operating devolatilization extruder having a liquids inlet        portion and a polymer melt or polymer flow outlet portion and at        least two sections that can be operated (a) at temperatures that        differ from each other, and (b) under pressures that differ from        each other, one of the at least two sections being disposed        upstream from the other of the at least two sections, the        devolatilization extruder having vapor collecting apparatus        adapted to collect volatiles formed in these at least two        sections;    -   operating said section disposed downstream at higher temperature        and lower pressure conditions than the temperature and pressure        conditions of said section disposed upstream, so that (a) a        flowable polymer melt or polymer flow of said polymer is formed        within the devolatilization extruder and released from the at        least one polymer melt or polymer flow outlet, and (b) volatiles        composed predominately of the solvent released from the polymer        in said at least two sections are collected by said vapor        collecting apparatus;    -   forming from said flowable polymer melt or polymer flow of said        polymer a downwardly oriented plug flow from at least one        orifice in a manifold or nozzle that is in proximity to a cooled        traveling planar member, said planar member being impervious to        cooling liquid and having an upper and lower surface, whereby        there is a gap between the lower portion of the orifice and said        upper surface, so that at least a portion of a plug of molten        unadulterated brominated anionic styrenic polymer either (i)        bridges said gap and forms a separate individual granule or        pastille on the upper surface of said planar member, or (ii)        freely drops from the lower portion of the orifice and falls        upon the upper surface of said planar member and forms an        individual granule or pastille on the upper surface of said        planar member, said traveling member being cooled by a mist or        spray of cooling liquid contacting the lower surface of said        planar member.

In this embodiment, the traveling planar member is preferably an endlessbelt impervious to cooling liquid, and more preferably is an endlesssteel belt. In addition, the mist or spray of cooling liquid ispreferably a mist or spray of cooling water. The mist or spray ispreferably applied to the lower surface of said planar member below theregion in which the separate individual granule or pastille is formed onthe upper surface of said planar member.

Brominated Styrenic Polymer

Styrenic polymers which are brominated to form the brominated styrenicpolymers recovered and/or pelletized pursuant to this invention are oneor more homopolymers and/or copolymers of one or more vinyl aromaticmonomers. Preferred vinyl aromatic monomers have the formula:H₂C═CR—Arwherein R is a hydrogen atom or an alkyl group having from 1 to 4 carbonatoms and Ar is an aromatic group (including alkyl-ring substitutedaromatic groups) of from 6 to 10 carbon atoms. Examples of such monomersare styrene, alpha-methylstyrene, ortho-methylstyrene,meta-methylstyrene, para-methylstyrene, para-ethylstyrene,isopropenyltoluene, vinylnaphthalene, isopropenylnaphthalene,vinylbiphenyl, vinylanthracene, the dimethylstyrenes, andtert-butylstyrene. Polystyrene is the preferred reactant. When thebrominated styrenic polymer is made by bromination of a copolymer of twoor more vinyl aromatic monomers, it is preferred that styrene be one ofthe monomers and that styrene comprise at least 50 weight percent andpreferably at least about 80 weight percent of the copolymerizable vinylaromatic monomers. The terms “vinylaromatic” and “styrenic” inconnection with monomer(s) or polymer(s) are used interchangeablyherein.

The aromatic pendant constituents of the styrenic polymer to bebrominated can be alkyl substituted or substituted by bromine orchlorine atoms, but preferably will not be so substituted. Typically,anionic styrenic polymers used to produce the brominated anionicstyrenic polymers used in the practice of this invention will have a GPCweight average molecular weight (M_(w)) in the range of about 2000 toabout 200,000, preferably in the range of about 3000 to about 10,000,and more preferably in the range of about 3000 to about 7000. Thepolydispersity of such anionic styrenic polymers will typically be inthe range of between 1 and about 4, and more preferably in the range ofbetween 1 and about 2. Typically, styrenic polymers produced by freeradical polymerization that are used to produce the brominated styrenicpolymers using a process of this invention will have a GPC weightaverage molecular weight (M_(w)) in the range of about 30,000 to about500,000, preferably in the range of about 50,000 to about 300,000, andmore preferably in the range of about 150,000 to about 250,000. Thepolydispersity of such styrenic polymers produced by free radicalpolymerization will typically be in the range of between 1 and about 10.All of the foregoing M_(w) and polydispersity values are based on gelpermeation chromatography (GPC) techniques which are hereinafterdescribed.

The polymers which are converted into unadulterated pelletized formpursuant to this invention are a single brominated styrenic polymer or ablend of two or more brominated styrenic polymers, preferably a singlebrominated anionic styrenic polymer or a blend of two or more brominatedanionic styrenic polymers. The foregoing blends can be of brominatedhomopolymers only, brominated copolymers only, or at least onebrominated homopolymer and at least one brominated copolymer of styrenicmonomer(s). Desirably, the bromine content of all such polymers is atleast about 50 percent by weight, although styrenic polymers with lowerbromine contents can readily be produced by this invention. Preferablypolymers of these types have a bromine content of at least about 60 wt%, more preferably of at least about 64 wt %, still more preferably atleast about 67 wt %, and even more preferably at least about 68 wt %.Usually the maximum bromine content is about 71 wt % with polymershaving a maximum of about 70 wt % bromine being more preferred. Asbetween homopolymers and copolymers, brominated polystyrene polymersmade by free radical polymerization are preferred and brominated anionicpolystyrene polymers are more preferred.

Methods for the production of styrenic polymers by free radicalpolymerization processes are well known in the art and reported in theliterature. See for example Encyclopedia of Polymer Science andEngineering, volume 16, John Wiley and Sons, 1989, pages 46-62. Forconvenience, the term “free-radically produced styrenic polymer” or“free-radically produced polystyrene”, whether in the singular orplural, is used in the claims to denote that the styrenic polymer orpolystyrene being referred to was produced previously before brominationby use of, or by another party's use of, a free radical polymerizationprocess. Methods for the preparation of anionic styrenic polymers suchas anionic polystyrene are also known in the art and reported in theliterature. See for example, U.S. Pat. Nos. 3,812,088; 4,200,713;4,442,273; 4,883,846; 5,391,655; 5,717,040; and 5,902,865, thedisclosures of which are incorporated herein by reference. An especiallypreferred method is described in commonly-owned U.S. Pat. No. 6,657,028,issued Dec. 2, 2003, the disclosure of which method is incorporatedherein by reference.

Bromination processes which can be used for producing a brominatedanionic styrenic polymer are disclosed in U.S. Pat. Nos. 5,677,390;5,686,538; 5,767,203; 5,852,131; 5,852,132; 5,916,978; 6,133,381;6,207,765; 6,232,393; 6,232,408; 6,235,831; 6,235,844; 6,326,439; and6,521,714 which disclosures are incorporated herein by reference.

In all embodiments of this invention the preferred brominated styrenicpolymers formed and/or used are brominated anionic styrenic polymers,and of the brominated anionic styrenic polymers, brominated anionicpolystyrene is especially preferred.

Typical properties of a desirable commercially-available brominatedpolystyrene for use in preparing the pellets of this invention, wherethe polystyrene used was produced by free radical polymerization,include the following:

Appearance/form—off-white powder or granules formed by powder compaction

Bromine Content—68.5 wt %

Tg(° C.)—182

Specific gravity (@23° C.)-2.15

TGA (TA instruments model 2950, 10° C./min. under N₂):

-   -   1% weight loss, ° C.-346    -   5% weight loss, ° C.-375    -   10% weight loss, ° C.-383    -   50% weight loss, ° C.-399    -   90% weight loss, ° C.-435        Such brominated polystyrene is presently available from        Albemarle Corporation under the designation SAYTEX® HP-7010P        flame retardant. A powder-compacted granular form of such        brominated polystyrene is presently available from Albemarle        Corporation under the designation SAYTEX® HP-7010G flame        retardant.

Typical properties of a preferred brominated anionic polystyrene for usein preparing the pellets of this invention include the following:

Appearance/form—white powder or pellet formed by melt extrusion ofpowder

Bromine Content—67 to 71 wt %

Melt flow index (220° C. 2.16 kg)—4 to 35 g/10 min

Tg(° C.)—170

Specific gravity (@23° C.)-2.2

TGA (TA instruments model 2950, 10° C./min. under N₂):

-   -   1% weight loss, ° C.-361    -   5% weight loss, ° C.-386    -   10% weight loss, ° C.-394    -   50% weight loss, ° C.-417    -   90% weight loss, ° C.-435        Methods for preparing brominated polystyrene having the above        properties are described in U.S. Pat. No. 6,521,714. Brominated        anionic polystyrene is presently available in the form of        granules from Albemarle Corporation under the designation        SAYTEX® HP 3010G flame retardant. Such granules are formed by        melt extrusion of powder and are not prepared by the process of        this invention. SAYTEX® HP 3010P flame retardant is the powder        form of brominated anionic polystyrene produced by Albemarle        Corporation.        Solvents

The solvents present in the solutions of brominated styrenic polymersused in the various embodiments of this invention can be any liquidsolvent that is capable of being vaporized at a temperature below thatat which the brominated styrenic polymer dissolved therein would beginto undergo thermal degradation, and that does not adversely react withthe brominated styrenic polymer dissolved therein. Typically the solventis composed of one or more halogenated solvents that have boilingtemperatures below about 150° C. at atmospheric pressures. Typicalhalogenated solvents are those in which each halogen atom is a bromineatom or a chlorine atom or in which the solvent contains at least onebromine atom and at least one chlorine atom. Less preferred are solventscontaining one or more halogen atoms other than bromine atoms and/orchlorine atoms. A feature of this invention is that the solvent can bethe solvent in which the brominated styrenic polymer was formed bybromination of a styrenic polymer in the presence of a Lewis acidcatalyst. Illustrative examples of such processes are set forth in thepatents cited at the outset of this specification. However if desired, asolvent exchange procedure can be used to replace the initial solventwith a different vaporizable solvent at any suitable stage prior tofeeding into a devolatilization extruder. The term “vaporizable” simplymeans that the solvent should boil at a temperature below that at whichthe particular brominated styrenic polymer dissolved therein would beginto undergo an unacceptable amount of thermal degradation. Thistemperature will of course vary from case to case depending upon suchfactors as the type of brominated styrenic polymer present in thesolvent, the length of time the solution is at a threshold decompositiontemperature, and the quality control specifications imposed upon thefinal brominated styrenic polymer product. Non-limiting examples ofsuitable organic solvents include dichloromethane, dibromomethane,bromochloromethane, bromotrichloromethane, chloroform, carbontetrachloride, 1,2-dibromoethane, 1,1-dibromoethane,1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromopropane,1-bromo-3-chloropropane, 1-bromobutane, 2-bromobutane,2-bromo-2-methylpropane, 1-bromopentane, 1-bromo-2-methylbutane,1-bromohexane, 1-bromoheptane, bromocyclohexane, and liquid isomers,homologs, or analogs thereof. Liquid mixtures of two or more suchcompounds can be used. Bromochloromethane is a particularly preferredsolvent. If a solvent exchange procedure is used, such halogenatedsolvent can be replaced for example by a vaporizable liquid aromatichydrocarbon solvent.

Drying and Concentrating Initial Solvent Solution

In the embodiments of this invention involving processes for recovery ofbrominated styrenic polymers as a melt or flow for subsequent use and inthe embodiments of this invention involving processes for pelletizingbrominated styrenic polymers where the solution contains some water, itis desirable to “dry” the solution by freeing it of most, if notessentially all, of the water. For example, when a reaction mixture isformed from Lewis acid-catalyzed bromination of a styrenic polymer in asuitable organic solvent such as halogenated hydrocarbon or halocarbonsolvent, the catalyst is typically deactivated by quenching the reactionmixture with an aqueous quenching solution such as water by itself.After a phase cut to separate the organic phase of brominated styrenicpolymer in organic solvent from the aqueous phase, some water typicallyremains in such organic phase. To remove such water the “wet” organicphase (i.e., organic phase which contains along with the brominatedstyrenic polymer, some residual amount of water, e.g., ca. 1500 ppm ofwater), is preferably passed through a coalescer to effect separation ofat least a large portion of the free water, e.g., to a level of ca. 300ppm or less of water). If the resultant “dried” solution of brominatedstyrenic polymer in the organic solvent contains less than about 40 wt %of brominated styrenic polymer, such solution is preferably subjected todistillation, more preferably a flash distillation, to remove organicsolvent as a collectable vapor phase along with any water retained bythe polymer solution. In this way a more concentrated essentiallyanhydrous organic solution containing at least about 50 wt % ofbrominated styrenic polymer is formed. Such more highly concentratedsolution is ideally suited for use as the feed to the devolatilizationextruder.

The technology for coalescing filtration, including coalescingfiltration for separating water from organic liquid systems, is wellknown and reported in the literature, and systems for separating waterfrom organic liquid systems are available from various commercialsuppliers. Suitable filter media for effecting such separations includefiberglass, ceramics, and sand. The use of a bed of sand is a preferredmedium for use in embodiments of the present invention in whichcoalescing filtration is to be employed.

Recovery of Brominated Styrenic Polymers from Solvent

In the various processes of this invention for recovering brominatedstyrenic polymers from a solution in an organic solvent, some of whichprocesses have been described above, the product as initially recoveredfrom the devolatilization extruder is in the form of a melt or is in atleast a soft flowable form. The melt can be cooled or allowed to cooland then can be converted (e.g., by molding) into various shapes orconfigurations for storage and shipment or it can be pulverized intoparticulate form or fine powder form. In order to convert the polymermelt or polymer flow directly into pelletized form, use of the processembodiment of this invention devoted to preparing pelletized brominatedstyrenic polymers is especially preferred. However, if desired, thepelletizing process described in commonly-owned published PCT patentapplication WO 2005/118245 can be used from dry powdered brominatedstyrenic polymer as pellets made by that process are of good quality.However, based on available test results, pellets made pursuant to thisinvention are even better than those produced according to WO2005/118245, especially in hardness and/or high crush strength.

Recovery of brominated styrenic polymers from solution by an embodimentof this invention involves selection and operation of a devolatilizationextruder in a suitable manner such as described herein so that thesolvent is vaporized in and can be, and preferably is, collected fromthe extruder. Preferably the recovered solvent is reused by recycling toa process in which styrenic polymer is brominated using a Lewis acidcatalyst. In an especially preferred embodiment of this invention aprocess is provided comprising conducting the bromination of a styrenicpolymer in a liquid phase reaction mixture under superatmosphericpressure in a closed reaction system so that gaseous hydrogen halide(HX, where X is a bromine or chlorine atom) coproduct is not releasedfrom said closed reaction system separately and apart from such reactionmixture until the reaction has been terminated by quenching the reactionmixture in an aqueous quenching medium which destroys the catalyst anddissolves the HX forming hydrobromic acid or if BrCl is used as thebrominating agent, hydrochloric acid. The organic phase containing thebrominated styrenic polymer and the aqueous phase containing the HX areseparated from each other by a phase separation procedure such assettling and draining off the lower phase or siphoning off the upperphase. Preferably additional aqueous washes are carried out to morecompletely remove residual HX and any inorganic salts that may bepresent. If desired, the organic phase may be subjected to coalescingfiltration to achieve essentially complete separation of the aqueousphase from the organic phase. After concentrating the organic phasecontaining the brominated styrenic polymer, the more concentratedorganic phase is then introduced into a devolatilization extruderwherein the solvent is vaporized and recovered, and a melt or polymerflow of the essentially solvent free brominated styrenic polymer isreleased from the extruder. In cases where HX in the aqueous phase isHBr, it is preferred to thereafter recover the bromine values from theaqueous phase by (i) steam stripping the aqueous phase to removeresidual organic solvent from the aqueous phase and thereby provide ahydrobromic acid product suitable for use or sale; (ii) converting theHBr in the aqueous phase to elemental bromine; or (iii) reacting the HBrwith an aqueous metallic base to produce a solution of a metal bromidesalt suitable for use or sale.

Thus in accordance with another embodiment of this invention there isprovided a process for the preparation of a brominated styrenic polymer,typically having a bromine content of at least about 50 wt %, andpreferably at least about 60 wt %, and still more preferably at leastabout 67 wt % in the form of a melt or polymer flow, which processcomprises:

-   -   brominating a styrenic polymer under superatmospheric pressure        in a vaporizable solvent and in the presence of a Lewis acid        bromination catalyst, and in a closed reaction system in which        substantially all of the hydrogen halide coproduct is retained        in the reaction mixture;    -   quenching the catalyst to thereby form (i) an organic phase        containing dissolved brominated styrenic polymer, and (ii) an        aqueous phase containing hydrogen halide;    -   separating phases (i) and (ii) from each other, using coalescing        filtration, if desired, to attain essentially complete        separation of phases, and if phase (i) has a viscosity less than        extrudable viscosity, concentrating organic phase of (i) to form        and admixture of extrudable viscosity, such concentration        preferably being accomplished by use of distillation or flash        distillation;    -   continuously introducing organic phase of (i) or admixture of        extrudable viscosity into the liquids inlet portion of an        operating devolatilization extruder having a liquids inlet        portion and a polymer melt or polymer flow outlet portion and at        least two sections that can be operated (a) at temperatures that        differ from each other, and (b) under pressures that differ from        each other, one of the at least two sections being disposed        upstream from the other of the at least two sections, the        devolatilization extruder having vapor collecting apparatus        adapted to collect volatiles formed in these at least two        sections; and    -   operating said section disposed downstream at higher temperature        and lower pressure conditions than the temperature and pressure        conditions of said section disposed upstream, so that (a) a        flowable polymer melt or polymer flow of said polymer is formed        within the devolatilization extruder and released from the at        least one polymer melt or polymer flow outlet, and (b) volatiles        composed predominately of the solvent released from the polymer        in said at least two sections can be, and preferably are,        collected by said vapor collecting apparatus, the polymer melt        or polymer flow of such brominated styrenic polymer leaving from        the outlet portion of the devolatilization extruder containing        an average of less than about 10,000 ppm (wt/wt), and preferably        less than about 5000 ppm (wt/wt), and still more preferably less        than about 1000 ppm (wt/wt) of the organic solvent during        steady-state operation.        The quenching in the above embodiment can be conducted in the        reactor in which a batch of the brominated styrenic polymer has        just been prepared or more preferably in a separate vessel. When        the bromination is conducted on a continuous basis, the        bromination reaction product is continuously transmitted while        under pressure into a separate vessel or zone and into contact        in such vessel or zone with an aqueous quenching medium,        preferably water. During the quenching the catalyst residues        tend to collect in the aqueous phase and essentially all of the        hydrogen halide is taken up in the water. After conducting the        phase separation between (i) and (ii) in the above embodiment        and before effecting the introduction into the liquids inlet        portion of the devolatilization extruder, it is preferable to        subject the organic phase of (i) to coalescing filtration in        order to remove entrained water containing dissolved salt(s)        from the organic phase containing the brominated styrenic        polymer.        Production of Pellets

Among the various embodiments of this invention is a process forproducing pelletized brominated styrenic polymers from an admixture ofbrominated styrenic polymer and a vaporizable solvent, which processcomprises:

-   -   optionally forming an admixture of extrudable viscosity        comprising brominated styrenic polymer and a vaporizable organic        solvent, preferably a vaporizable halogenated organic solvent,        from a less concentrated admixture thereof having a brominated        styrenic polymer content of 40 wt % or less, the vaporizable        organic solvent preferably being a halogenated solvent in which        the brominated styrenic polymer was formed by bromination of a        styrenic polymer in the presence of a Lewis acid catalyst;    -   continuously introducing an admixture of extrudable viscosity        comprising brominated styrenic polymer and a vaporizable organic        solvent, into the liquids inlet portion of an operating        devolatilization extruder having a liquids inlet portion and a        polymer melt or polymer flow outlet portion and at least two        sections that can be operated (a) at temperatures that differ        from each other, and (b) under pressures that differ from each        other, one of the at least two sections being disposed upstream        from the other of the at least two sections, the        devolatilization extruder having vapor collecting apparatus        adapted to collect volatiles formed in these at least two        sections;    -   operating said section that is disposed downstream at higher        temperature and lower pressure conditions than the temperature        and pressure conditions of said section that is disposed        upstream, so that (a) a flowable melt or flow of said polymer is        formed within the devolatilization extruder and forcibly        released from the polymer melt or polymer flow outlet, and (b)        volatiles composed predominately of the solvent released from        the polymer in said at least two sections can be, and preferably        are, collected by said vapor collecting apparatus, the polymer        melt or polymer flow of such brominated styrenic polymer that        exits from the outlet portion of the devolatilization extruder        containing an average of less than about 10,000 ppm (wt/wt), and        preferably less than about 5000 ppm (wt/wt), and still more        preferably less than about 1000 ppm (wt/wt) of the organic        solvent in steady-state operation;    -   having the polymer melt or polymer flow from the        devolatilization extruder pass through a die to produce        traveling strand(s) of extruded polymer melt or polymer flow;    -   enabling and/or causing such traveling strand(s) to solidify        (e.g., by enabling and/or causing a sufficient reduction in the        temperature of the traveling strand(s)) and be broken,        subdivided, or otherwise converted into pellets of the        brominated styrenic polymer (e.g., by providing a vacuum system        under the conveyor belt or web to draw air downwardly over and        around the strands on the web, and by applying jets of water        downwardly onto the strands traveling on the conveyor belt or        web of sufficient force to cause at least some breakage of the        strands, the porosity of the belt or web allowing the water to        pass downwardly through the web but of fine enough porosity to        retain the broken, subdivided, or pelletized polymer strands on        the belt or web and enabling and/or causing broken, subdivided,        or pelletized polymer strands to fall from the belt or web into        a size classifier whereby the impact from the fall may cause        some additional breakage of strand pieces to occur);    -   subjecting the pellets to size classification (e.g., by use of        appropriate screening techniques) to remove and recover from        such product (a) oversized particles, if any, and (b) fines, if        any, that may be present in such product.        In the above process it is preferred to collect oversized        particles and fines that may result from the size classification        and recycle them for example into the liquids inlet portion of        the devolatilization extruder, to any other suitable inlet in an        upstream portion of such extruder, or to the polymer melt or        polymer flow passing into the die so that the particles and        fines become part of the polymer melt or polymer flow. When        using the above optional first step, it is preferable to subject        the less concentrated solution to flash distillation to thereby        form the desired more concentrated solution, and also to recycle        halogenated solvent collected by the vapor collecting apparatus        of the devolatilization extruder as at least part of the solvent        used in ensuing bromination of styrenic polymer.

Still another embodiment of this invention is a process for producingpelletized brominated styrenic polymers, which process comprises:

-   -   feeding a solution containing at least about 50 wt % of        brominated styrenic polymer dissolved a vaporizable solvent into        a devolatilization extruder that is adapted and operated to        separate vaporizable solvent from said polymer and form as        extrudate a polymer melt or polymer flow of said polymer;    -   having the extrudate pass through a die to thereby form one or        more traveling strands of molten unadulterated brominated        styrenic polymer, preferably unadulterated anionic styrenic        polymer; and    -   pelletizing such strands by enabling and/or causing such        traveling strand(s) to solidify (e.g., by enabling and/or        causing a sufficient reduction in the temperature of the        traveling strand(s)) and be broken, subdivided, or otherwise        converted into pellets of the brominated styrenic polymer (e.g.,        by providing a vacuum system under the conveyor belt or web to        draw air downwardly over and around the strands on the web, and        by applying jets of water downwardly onto the strands traveling        on the conveyor belt or web of sufficient force to cause at        least some breakage of the strands, the porosity of the belt or        web allowing the water to pass downwardly through the web but of        fine enough porosity to retain the broken, subdivided, or        pelletized polymer strands on the belt or web and enabling        and/or causing broken, subdivided, or pelletized polymer strands        to fall from the belt or web into a size classifier whereby the        impact from the fall may cause some additional breakage of        strand pieces to occur); and    -   subjecting the pellets to size classification (e.g., by use of        appropriate screening techniques) to remove and recover from        such product (a) oversized particles, if any, and (b) fines, if        any, that may be present in such product.

Yet another embodiment of this invention is a process for thepreparation of a pelletized brominated styrenic polymer typically havinga bromine content of at least about 50 wt %, and preferably at leastabout 60 wt %, and still more preferably at least about 67 wt % in theform of a polymer melt or polymer flow, which process comprises:

-   -   brominating a styrenic polymer under superatmospheric pressure        in a vaporizable solvent and in the presence of a Lewis acid        bromination catalyst, and in a closed reaction system in which        substantially all of the hydrogen halide coproduct is retained        in the reaction mixture;    -   quenching the catalyst to thereby form (i) an organic phase        containing dissolved brominated styrenic polymer having a        bromine content as aforesaid and (ii) an aqueous phase        containing hydrogen halide;    -   separating such phases from each other, and preferably        subjecting the organic phase containing dissolved brominated        styrenic polymer to a coalescing filtration;    -   concentrating the organic phase containing dissolved brominated        styrenic polymer to a viscosity suitable for use in a        devolatilization extruder;    -   continuously introducing organic phase containing dissolved        brominated styrenic polymer into the liquids inlet portion of an        operating devolatilization extruder having a liquids inlet        portion and a polymer melt or polymer flow outlet portion and at        least two sections that can be operated (a) at temperatures that        differ from each other, and (b) under pressures that differ from        each other, one of the at least two sections being disposed        upstream from the other of the at least two sections, the        devolatilization extruder having vapor collecting apparatus        adapted to collect volatiles formed in these at least two        sections;    -   operating said section disposed downstream at higher temperature        and lower pressure conditions than the temperature and pressure        conditions of said section disposed upstream, so that (a) a        flowable polymer melt or polymer flow of said polymer is formed        within the devolatilization extruder and released from the        polymer melt or polymer flow outlet, and (b) volatiles composed        predominately of the solvent released from the polymer in said        at least two sections can be, and preferably are, collected by        said vapor collecting apparatus, the polymer melt or polymer        flow of such brominated styrenic polymer that has exited from        the outlet portion of the devolatilization extruder containing        an average of less than about 10,000 ppm (wt/wt), and preferably        less than about 5000 ppm (wt/wt), and still more preferably less        than about 1000 ppm (wt/wt) of the organic solvent in        steady-state operation;    -   having the polymer melt or polymer flow from the        devolatilization extruder pass through a die to produce        traveling strand(s) of extruded polymer melt or flow;    -   enabling and/or causing such traveling strand(s) to solidify        (e.g., by enabling and/or causing a sufficient reduction in the        temperature of the traveling strand(s)) and be broken,        subdivided, or otherwise converted into pellets of the        brominated styrenic polymer (e.g., by providing a vacuum system        under the conveyor belt or web to draw air downwardly over and        around the strands on the web, and by applying jets of water        downwardly onto the strands traveling on the conveyor belt or        web of sufficient force to cause at least some breakage of the        strands, the porosity of the belt or web allowing the water to        pass downwardly through the web but of fine enough porosity to        retain the broken, subdivided, or pelletized polymer strands on        the belt or web and enabling and/or causing broken, subdivided,        or pelletized polymer strands to fall from the belt or web into        a size classifier whereby the impact from the fall may cause        some additional breakage of strand pieces to occur); and    -   subjecting the pellets to size classification (e.g., by use of        appropriate screening techniques) to remove and recover from        such product (a) oversized particles, if any, and (b) fines, if        any, that may be present in such product.        Devolatilization Extruder

In conducting the various processes of this invention, commerciallyavailable devolatilization extruders can be successfully adapted for usein practicing such processes. The extruder can be of single screwconfiguration, co-rotating twin screw configuration, or counter-rotatingtwin screw configuration. Twin screw non-intermeshing counter-rotatingdevolatilization extruders are preferred. The machine should be equippedwith a liquids inlet portion at the feed portion of the extruder and apolymer melt or flow outlet portion at the discharge portion of theextruder. It should also have along the length of the screw(s) at leasttwo housing sections, and preferably four or more housing sections, thatcan be independently operated (a) at temperatures (preferably adjustabletemperatures) that differ from each other and (b) pressures (preferablyadjustable pressures) that differ from each other. At least some of themidstream or downstream sections must be able, and preferably all of thesections should be able, to provide internal temperatures high enough toform a polymer melt or polymer flow of the brominated styrenicpolymer(s) to be used in the machine. Typically varying temperatures ofup to about 350° C. will suffice. The heat generated by friction withinthe machine should of course be taken into consideration in setting thetemperatures of the segments or zones in which the polymer melt orpolymer flow is being processed by the machine. Also at least some ofthe midstream or downstream sections, and preferably all of thesections, should be adapted to independently operate at reducedpressures in the range of about 1 to about 500 mm of Hg. Thedevolatilization extruder should be used in conjunction with vaporcollecting apparatus adapted to collect all volatiles formed in each ofthe sections. The pitch of the forward-flighted screw elements should beadapted to provide a continuous flow of the contents of the extruder tomaximize production rate. If necessary, or desirable, because of thecharacteristics of the particular brominated styrenic polymer to beprocessed, the screw elements may also contain reverse-flighted elementsfor more intensive mixing and/or cylindrical elements to create a seal.The manufacturers of such machines can adapt the type and/or pitch ofthe screws to achieve satisfactory rates of flow and mixing once theyare provided with samples of the particular brominated styrenic polymerto be processed in a suitable devolatilization extruder. Continuousoperation of the devolatilization extruder is the especially preferredmode of operation, although it is possible to practice at least some ofthe processes of this invention, e.g., processes for recovery ofbrominated styrenic polymers from solutions, as batch operations.

Use may be made of devolatilization extruder machines provided bycommercial manufacturers of such equipment.

For anyone unfamiliar with extruders including devolatilizationextruders, their design and their operation, reference may be made toChris Rauwendaal, Polymer Extrusion, 4th Edition, Hanser GardnerPublications, Inc., Cincinnati, Ohio for further details known andavailable to those of ordinary skill in that art. See also U.S. Pat.Nos. 3,082,816 and 4,110,843.

Illustrative Preferred Process Embodiment

A devolatilization extruder is operated at a suitable temperature andpressure profile to cause the brominated anionic styrenic polymer to besubstantially freed of solvent in the initial upstream section(s) and tobecome at least highly softened if not molten in the midstream and/ordownstream section(s). The temperature profile used will thus varysomewhat depending on the makeup of the brominated anionic styrenicpolymer being processed.

The extrudate from the machine is passed through a die plate and theresultant continuous strands are allowed to drop onto a moving porousconveyor belt.

The contents of the belt and any former contents of the conveyor beltthat may be emerging from the end of the conveyor belt are caused todrop into a classifier which separates the pellets and the fines fromeach other. Such droppage onto the classifier may also cause somebreakage to occur. The classifier can include, for example, anessentially horizontally disposed mesh which is caused to vibrate backand forth longitudinally. A particularly suitable machine of this typeis a Vibratory Classifier such as is available from The Witte Company,Inc.

In a typical operation, the conveyor belt used is about 14 feet inlength and is operated at a speed in the range of about 100 to about 200ft/min. The forced air and the water used in the misting of the strandsare typically at ambient room temperatures, but can be heated if desiredso as to reduce heat shock. The distance of the drop from the end of theconveyor belt to the screen of the classifier is typically in the rangeof about 18 to about 36 inches.

In any of the properly conducted pelletizing processes of this inventionusing as the feed to the devolatilization extruder a 50 wt % solution inbromochloromethane of brominated anionic polystyrene, which brominatedanionic polystyrene has a bromine content of at least 50 wt %(preferably at least 60 wt %, and more preferably at least 67 wt %), itshould be possible to produce a product in which no more than about 5 wt%, preferably no more than about 3 wt %, and more preferably no morethan about 1 wt % are fines or dusts that pass through a standard U.S.No. 40 sieve. Thus, the pelletizing processes of this invention arehighly efficient; only small amounts of such fines are collected andpreferably recycled in the overall pelletizing operation.

Turning now to the Drawings, FIG. 1 depicts in block diagram format manyof the steps included in preferred process operations of this inventionfrom which some or all of the depicted steps may be used, depending uponthe particular embodiment being utilized. The sequence shown in FIG. 1is typical, but suitable changes or additions can be made in thesequence such as insertion of separation steps, washing steps, or otherlike processing steps, not shown in FIG. 1. Thus, as long asdevolatilization as at IX is conducted, an embodiment of this inventioncan start at any stage at or above IX, and stages above and/or below IXcan be inserted or omitted from the sequence depicted as long as aresult pursuant to this invention is achieved. As seen from FIG. 1, someembodiments of this invention start with I, bromination of styrenicpolymer to form brominated styrenic polymer. Optionally hydrogen halide(HBr or HCl) co-product may be removed from the reaction mixture.Alternatively the hydrogen halide co-product is kept in the reactionmixture to serve as a co-solvent. When the desired extent of brominationhas been achieved, the aromatic bromination reaction is terminated as atII, by addition of a suitable quantity of water to deactivate thecatalyst. When the hydrogen halide co-product has been kept with thereaction mixture, this catalyst deactivation is accomplished in a closedsystem operating under pressure to retain the hydrogen halide co-productwith the reaction mixture when such technique is being used instead ofventing and collecting this co-product earlier in the operation. Ineither case the reaction mixture with all or only a portion of theco-product HX is quenched, with water or water containing othercomponents such sodium sulfite as at III. The hydrogen halide can berecovered as hydrobromic acid or hydrochloric acid. Use of the sequenceof II and III is preferred. However, it is possible to eliminate II andconduct quenching as at III by pumping the reaction mixture into wateror aqueous sodium sulfite. The aqueous and organic phases are separatedas at IV. The organic phase containing the brominated styrenic polymercan then be washed with aqueous base such as aqueous sodium hydroxidesolution as at V, to remove residual HBr and/or HCl.

In some preferred embodiments, it is desirable to subject the organicphase which typically consists essentially of a solution of up to about40 wt % of brominated styrenic polymer in organic solvent plus someresidual water and salts, to coalescing filtration as at VI, to removeentrained water and dissolved salts from the organic phase. In someembodiments of this invention the processing of such organic phase iscontinued. In other embodiments an organic phase typically consistingessentially of a solution of up to about 40 wt % of brominated styrenicpolymer in organic solvent and which may or may not have been subjectedto coalescing filtration, is used as a starting material fordevolatilizing extrusion. In any such case, such an organic phase isconcentrated as at VII, to form an admixture of extrudable viscositytypically by distillation or flash distillation to remove a suitableportion of the organic solvent from the organic phase mixture.Preferably, solvent removed from the mixture is recovered for reuse. Inembodiments where an initial organic phase mixture is of a brominatedstyrenic polymer of sufficiently high molecular weight as to yield amixture which already is of extrudable viscosity, such concentrationstep of VII may be eliminated. Before processing the admixture ofextrudable viscosity to effect devolatilization in a devolatilizationextruder, it is desirable to preheat the admixture as at VIII. Suchpreheating can be conducted in a devolatilization extruder if equippedwith preheating section, or in a separate preheater vessel or zone ifthe devolatilization extruder is not equipped with a preheating section.Such preheating typically facilitates operation of the devolatilizationextruder, and is thus preferably utilized in the process.

In some embodiments of this invention the processing of such admixtureof extrudable viscosity is continued after conducting V, VI, or VII,whereas in other embodiments such an admixture is used as a statingmaterial. In any such case, an admixture of extrudable viscosity,preferably after at least formed via concentration as at VII, isprocessed in a devolatilization extruder as at IX, to form a melt orflow of brominated styrenic polymer and a separate vapor phase oforganic solvent which preferably is recovered and condensed for reuse asa solvent. Then the melt or flow is subjected to product recovery as atX-A or subjected to pelletizing as at X-B, or a portion of the melt issubjected to product recovery as at X-A and another portion (typicallyall the rest of the melt or flow) is subjected to pelletizing as at X-B.Product recovery as at X-A can be as simple as collecting or recoveringmelt or flow of brominated styrenic polymer from a devolatilizationextruder. FIGS. 2 and 3 illustrate a preferred way of carrying out thepelletizing operation.

Referring now to a preferred system involving pellet formation asschematically depicted in FIGS. 2 (top view) and 3 (side view) whereinlike numerals depict like parts, an admixture of extrudable viscositycomprising brominated styrenic polymer, preferably brominated anionicstyrenic polymer, typically containing at least 50 wt % of bromine and asolvent, preferably a halogenated solvent, is fed from line 10 intoinlet 12 of devolatilization extruder 11 equipped with a preheatersection (not shown). If the devolatilization extruder 11 is not soequipped, the admixture is preferably fed to a separate preheater orpreheater zone (not shown). In either such case the admixture ispreferably preheated to a temperature in the range of about 165 to about185° C., and then processed in the devolatilization extruder so that theadmixture is devolatilized, e.g., substantially freed of halogenatedsolvent and other volatile substances that may be present, byapplication of sufficient heat and reduced pressure. Depending on thedesign of devolatilization extruder 11, most of the volatiles may bedischarged through a vent located to the rear of inlet 12. In any event,further downstream in devolatilization extruder 11, the contents of theextruder achieve a flowable semi-solid state as a polymer melt and/or apolymer flow of the brominated styrenic polymer and the melt or flow isdischarged through die 18 whereby strands, typically continuous strands,of the polymer are extruded from the die onto moving conveyor belt 20.In the system depicted, belt 20 is upwardly inclined such that theremote end of the upper portion of the belt is typically about 18 toabout 36 inches above vibratory classifier 30. Spray system denotedgenerally as 33 forms and dispenses a mist or spray of water onto thehot polymer strands on the upper portion of belt 20 which is travelingin the direction shown by arrow 35. The cooled strands are then carriedby belt 20 under air knives 37,37 which cut or break at least a portionof the strands into pellets. At the underside of belt 20 in proximity tothe location of air knives 37,37 are vacuum inlets 39,39 of aconventional vacuum manifold system (not shown) which draws off residualwater and fines from the underside of belt 20. The resultant pellets aredischarged at the upper outer end of belt 20 and fall under theinfluence of gravity onto the operative upper surface of classifier 30which can be a vibratory classifier. The impact of the fall can resultin formation of addition pellets through breakage of larger piecesfalling from belt 20. Thus the pellets in the system depicted in FIGS. 2and 3 are mainly formed in the region extending from the air knives37,37 to and including classifier 30. Fines are separated by andcollected within classifier 30 which continuously transfers the pelletsremaining after the separation onto transfer device 40 such as asegmented conveyor or bucket elevator disposed to receive and convey thepellets forwardly and upwardly to an elevation suitable for feeding thepellets to a suitable heavy duty packaging container 50, such as aSupersack or Gaylord container. If any fines are formed in suchpackaging step due to pellet breakage, it can be minimized or eliminatedby reduction in the height of the fall from the transfer device to thepackaging container.

FIG. 4 of the drawings illustrates a preferred sequence of stepsutilizing an overall process of this invention in which granules orpastilles of unadulterated brominated styrenic polymers are produced.The above description relative to FIG. 1 as regards forming pelletsapplies equally well to FIG. 4, except for the last step. In FIG. 4, thelast step involves forming granules or pastilles using appropriateprocedures and apparatus.

The combination of devolatilization followed by forming granules orpastilles using apparatus such as is available in the open marketprovides a number of important technical and economic advantages. In thefirst place, use of this combination of operations eliminates the needfor a very large scale (e.g., 16,000 gallon) precipitation vessel inwhich the brominated anionic styrenic polymer is precipitated from thereaction mass in hot water. Also eliminated are other associated itemssuch as a centrifuge for recovering the solids from the liquid phase anda large scale dryer for drying the product. Elimination of such largescale equipment also enables the overall process to be operated in asmaller space. In addition, operating costs including heat energyrequirements are significantly reduced, substantial portions of thesolvent used in the process (i.e., that coming from the devolatilizationextruder) can be recycled without drying, and the overall process hasthe additional capability of purging volatile impurities or coproductsfrom the heavy ends formed in the process. For example, duringcontinuous or repetitive batch operations, a small portion of thesolvent, preferably bromochloromethane, becomes converted intodibromomethane and it is highly advantageous to purge this material atleast periodically from the solvent being recycled in the process.

Illustrative of commercially-available apparatus that can be adapted foruse in forming the granules or pastilles is the system available fromKaiser Steel Belt Systems GmbH designated as Pastillation SystemRollomat®. Equipment of this type and its operation is not onlydescribed in promotional material available from Kaiser Steel BeltSystems GmbH, but also in U.S. Pat. Nos. 5,198,233 and 5,278,132.

Analytical Procedures

If deemed necessary or desirable, any reliable analytical procedure suchas reported in the literature can be employed in determining suchanalysis or properties. In any doubtful or disputed case, the followingprocedures are recommended:

1) Bromine Content—Since brominated styrenic polymers have good, or atleast satisfactory, solubility in solvents such as tetrahydrofuran(THF), the determination of the total bromine content for a brominatedstyrenic polymer is easily accomplished by using conventional X-RayFluorescence techniques. The sample analyzed is a dilute sample, say0.1±0.05 g brominated polystyrene in 60 mL THF. The XRF spectrometer canbe a Phillips PW1480 Spectrometer. A standardized solution ofbromobenzene in THF is used as the calibration standard.

2) Crush Strength—The Crush Strength Test utilizes a Sintech® 1/Scompression apparatus (MTS Systems Corporation, Edenprairie, Minn.)equipped with Testworks software, which software is installed in the 1/Scompression apparatus as supplied by MTS Systems Corporation. The 1/Scompression apparatus includes a horizontal load cell interfaced with acomputer, a digital micrometer also interfaced with the computer, and avertical screw-driven piston that is disposed above the load cell andadapted to apply a downward force perpendicular to the load cell. Theprocedure for measuring crush strength involves measuring the length ofthe pellet with the micrometer to provide a digitized input to thecomputer. Next the pellet is placed on its end on the load cell with thepiston in contact with the upper edge of the pellet. Then the apparatusis activated whereby the piston commences applying a progressivelyincreasing downward force to the pellet. At the same time, the load cellcontinuously measures the downward force being applied to the pellet,and the input of such measurements is transmitted to the computer. Whenthe force being applied reaches the point where the amount of forcesuddenly decreases to 10% of the immediately preceding force, the pellethas reached the breaking point, and the application of the force isimmediately terminated by the software program. From the inputs to thecomputer, two values are provided, namely the pounds of force at thebreaking point of the pellet, and the pounds of force per inch of lengthof the pellet at the breaking point. Thus the greater the force applied,the greater the crush strength. In the test 13 pellets are selected atrandom and used in the test. The only qualification is that the selectedpellets should have flat end portions so as to rest flatly on, and standvertically in, the load cell and with the flat upper end fitting flatlyagainst the lower surface of the piston.

3) Molecular Weight and Polydispersity—Molecular weight values ofstyrenic polymers are obtained by GPC using a Waters model 510 HPLC pumpand, as detectors, a Waters Refractive Index Detector, Model 410 and aPrecision Detector Light Scattering Detector, Model PD2000, orequivalent equipment. The columns are Waters, μStyragel, 500 Å, 10,000 Åand 100,000 Å. The autosampler is a Shimadzu, Model Sil 9A. Apolystyrene standard (M_(w)=185,000) is routinely used to verify theaccuracy of the light scattering data. The solvent used istetrahydrofuran, HPLC grade. The test procedure used entails dissolving0.015-0.020 g of sample in 10 mL of THF. An aliquot of this solution isfiltered and 50 μL is injected on the columns. The separation isanalyzed using software provided by Precision Detectors for the PD 2000Light Scattering Detector. The instrument provides results in terms ofweight average molecular weight and also in terms of number averagemolecular weight. Thus, to obtain a value for polydispersity, the valuefor weight average molecular weight is divided by the value for numberaverage molecular weight.

4) To determine the amount of organic solvent retained in a brominatedstyrenic polymer sample, proton NMR spectra are acquired using a BrukerDPX 400 MHZ instrument for solutions of about 20 wt % brominatedstyrenic polymer in 5/2 volume ratio carbon disulfide/dichloromethane-d₂(one 30 degree pulse experiment, 8 scans and 15 second pulse delay). Theintegrals of the brominated styrenic polymer are obtained along with theintegral(s) for the organic solvent component. Using the appropriatemolecular weight values with such integral(s), the amount of the organicsolvent in the polymer is calculated.

Continuous Processes

While the processes of this invention can be conducted as batchprocesses wherein a given quantity of feed materials are processed andthen the operation is shut down, it is preferred to conduct theprocesses of this invention on a continuous basis where onlyperiodically is the operation shut down e.g., for equipment repair ormaintenance. Preferred continuous processes of this invention produceeither highly pure melts or flows of brominated free radical styrenicpolymer or highly pure pellets of brominated free radical styrenicpolymer. Especially preferred continuous processes of this inventionproduce either highly pure melts or flows of brominated anionic styrenicpolymer or highly pure pellets of brominated anionic styrenic polymer.Common to these continuous processes are some or all of the operationsdescribed in block diagram form in FIG. 1.

Pellets of the Invention

Pursuant to this invention, pelletized brominated styrenic polymers areproduced having little, if any, fine particles or dusts.

Novel pellets of this invention are composed of unadulterated brominatedanionic styrenic polymer, preferably unadulterated brominated anionicpolystyrene, having the following characteristics:

-   A) a bromine content of at least about 50 wt %, preferably at least    about 60 wt %, more preferably at least about 64 wt %, and still    more preferably in the range of about 67 to about 71 wt %;-   B) an average crush strength in the Crush Strength Test of at least    about 28 pounds per square inch, and preferably of at least about 32    pounds per square inch;-   C) a particle size range in which at least about 70 wt %, and    preferably at least about 75 wt %, of the pellets are retained on a    standard U.S. Pat. No. 40 sieve and no more than about 30 wt % and    preferably no more than about 25 wt %, are retained on a standard    U.S. Pat. No. 5 sieve.    More preferably at least about 80 wt %, still more preferably at    least about 85 wt %, and even more preferably at least about 90 wt    %, of the pellets are retained on a standard U.S. No. 40 sieve and,    respectively, more preferably no more than about 20 wt %, still more    preferably no more than about 15 wt %, and even more preferably no    more than about 10 wt %, are retained on a standard U.S. No. 5    sieve.    Granules or Pastilles Producible by Use of this Invention

To simulate a process of this invention, pastilles were produced andsubjected to tests to determine their crush strength. Using a Rollormatpastillation system, (Kaiser Steel Belt Systems) brominated anionicpolystyrene having a bromine content of approximately 68% and a meltflow index at 220° C. and 2.16 kilogram load of 4 to 35 grams per 10minutes was subjected to pastillation. Substantially uniform pastilleswere formed and solidified on the water-cooled traveling steel belt. Asample of these pastilles was collected for determination of physicalproperties. In particular, tests were conducted to measure both theheight of 13 randomly selected pastilles produced in the process justdescribed and the crush strength of the selected pastilles. Theapparatus used in these tests was a Sintech 1/S instrument. Theprocedure used involved the following:

-   1) randomly selecting 13 pastilles from the sample undergoing the    test and measuring the height of each pastille from its flat base to    the peak of its dome;-   2) placing a pastille on the stationary unpadded steel plate of the    instrument such that the flat surface of the pastille rests on the    steel plate with the peak of the dome of the pastille directly below    the moveable crosshead of the instrument upon which a 50 pound load    cell is attached. Attached to the load cell is a cylindrical shaft    which is flat on its lower end that will come in direct contact with    the peak of the dome of the pastille;-   3) lowering the crosshead to within 0.002 inch of the peak of the    dome;-   4) lowering the crosshead by the motorized screw drive of the    instrument at the rate of 0.2 inch per minute until the pastille is    crushed at which point the maximum load is recorded, and the crush    strength in pounds per inch is calculated.    The above procedure is repeated individually with each of the 13    randomly selected pastilles from the sample of pastilles undergoing    the test. The crush strength is determined in each of the respective    13 cases by dividing the maximum load (in pounds) by the height (in    the fraction of an inch) of the respective pastille subjected to the    test.

Table 1 summarizes the results of the 13 individual tests, the averagevalues achieved, the standard deviations of the values achieved, and theminimum and maximum values achieved in the test. In Table 1, thegranules or pastilles are referred to simply as pastilles for economy ofspace. The abbreviations used and their full meaning are as follows: in.stands for inch; lbs stands for pounds force; Avg. stands for average;Std. Dev. stands for standard deviation; Min. stands for minimum; andMax. stands for maximum.

TABLE 1 Pastille Height, Peak Load Applied, Energy to Crush, PastilleNo. inches pounds lbs/in. 1 0.207 12.97 62.66 2 0.213 7.56 35.49 3 0.21914.52 66.30 4 0.208 10.23 49.18 5 0.213 9.26 43.47 6 0.199 8.00 40.20 70.224 7.34 32.77 8 0.207 14.67 70.87 9 0.200 10.08 50.40 10 0.214 10.2347.80 11 0.204 10.00 49.02 12 0.219 7.85 35.84 13 0.220 7.19 32.68Average 0.211 9.99 47.44 Std. Dev. 0.008 2.60 12.68 Min. 0.199 7.19 32.7Max. 0.224 14.67 70.9Use of the Pellets or the Granules or Pastilles as Flame Retardants

The pellets of this invention and the granules/pastilles producedpursuant to this invention can be used as flame retardants in a widevariety of thermoplastic polymers. Among such polymers are thermoplasticpolyesters, such as polyethylene terephthalate, polybutyleneterephthalate, polytrimethylene terephthalate, polycyclohexyleneterephthalate, etc.; thermoplastic polyamides, such as nylon 6, nylon6,6, nylon 6,12, etc.; polycarbonates; polyphenylene oxides, such aspoly(2,6-dimethylphenylene oxide); polysulphones; polystyrene or otherstyrenic homopolymers; copolymers of two or more styrenic monomers suchas copolymers of styrene, vinyltoluene, ethylstyrene, tert-butylstyrene,α-methylstyrene, vinylnaphthalene, etc.; rubber-modified vinylaromatichomopolymers or copolymers (e.g., high impact polystyrene); acrylate ormethacrylate polymers such as ethylene-methylacrylate,ethylene-ethylacrylate, ethylene-butylacrylate,poly(methylmethacrylate), etc.; ethylene-vinylacetate copolymers;acrylonitrile-based copolymers and terpolymers such asacrylonitrile-butadiene-styrene (ABS) and styrene-acrylonitrile (SAN),etc.; polyolefins, such as polyethylene, polypropylene, poly-(1-butene),and copolymers of ethylene with one or more higher vinyl olefins such aspropylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene; andblends, alloys, or composites of different polymers such as for examplea blend of poly(2,6-dimethylphenylene oxide) and polystyrene, a blend ofpolycarbonate and polystyrene, and similar blends. Additional polymersthat can be flame retarded by use therewith of pelletized flameretardant additives of this invention include rubbery block copolymerssuch as styrene-ethylene-ethylene-styrene,styrene-ethylene-propylene-styrene, styrene-ethylene-butylene-styrene,etc.; polyurethanes; epoxy resins; phenolic resins; elastomers such asnatural rubber, butyl rubber, GRS, GRN, EPDM, etc; polysiloxanes; andthe like. Further, the polymer may be, where appropriate, cross-linkedby chemical means or by radiation. A large number of flameretardant-free polymers suitable for use in the practice of thisinvention can be obtained from a number of commercial sources.

A preferred group of substrate polymers that can be effectively flameretarded by use of the pellets of this invention are polyesters.Thermoplastic polyesters, often referred to as polyalkyleneterephthalates, are reaction products of aromatic dicarboxylic acid orreactive derivatives thereof, such as methyl esters or anhydrides, andaliphatic, cycloaliphatic, or araliphatic diols, and mixtures of suchreaction products. Examples of such thermoplastic polyesters includepolyethylene terephthalate, polypropylene terephthalate, polybutyleneterephthalate, polycyclohexylene dimethylene terephthalate, and relatedcopolyesters and blends, including blends of one or more thermoplasticpolyesters with one or more other thermoplastic polymers such aspolycarbonates, and especially aromatic polycarbonates.

Preferred thermoplastic polyesters contain at least 80% by weight andpreferably at least 90% by weight, based on the dicarboxylic acidcomponent, of terephthalic acid and at least 80% by weight andpreferably at least 90% by weight, based on the diol component, ofethylene glycol and/or 1,4-butanediol units.

In addition to terephthalic acid units, the preferred thermoplasticpolyesters may contain up to 20 mole % and preferably up to 10 mole % ofunits of other aromatic or cycloaliphatic C₈₋₁₄ dicarboxylic acids oraliphatic C₄₋₁₂ dicarboxylic acids, such as, for example, units ofphthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid,4,4′-diphenyl dicarboxylic acid, succinic acid, adipic acid, sebacicacid, azelaic acid, or cyclohexane diacetic acid.

In addition to ethylene glycol and 1,4-butanediol units, the preferredthermoplastic polyesters may contain up to 20 mole % and preferably upto 10 mole % of other aliphatic C₃₋₁₂ diols or cycloaliphatic C₆₋₁₂diols, such as, for example, units of 1,3-propanediol,2-ethylpropane-1,3-diol, neopentyl glycol, 1,5-pentanediol,1,6-hexanediol, 1,4-cyclohexane-dimethanol, 3-ethylpentane-2,4-diol,2-methylpentane-2,4-diol,2,2,3-trimethylpentane-1,3-diol,2-ethylhexane-1,3-diol,2,2-diethylpropane-1,3-diol,2,5-hexanediol,2,2-bis(4-hydroxy-cyclohexyl)propane,2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane,2,2-bis[4-(2-hydroxy-ethoxy)phenyl]propane, or2,2-bis-[4-hydroxypropoxy)phenyl]propane.

Polyalkylene terephthalates may be branched by incorporation ofrelatively small quantities of trihydric or tetrahydric alcohols ortribasic or tetrabasic carboxylic acids. In this connection see, forexample, U.S. Pat. No. 3,692,744. Examples of preferred branching agentsare trimesic acid, trimellitic acid, trimethylol ethane and propane andpentaerythritol.

Particularly preferred thermoplastic polyesters are those producedsolely from terephthalic acid or a reactive derivative thereof such as adialkyl ester, and ethylene glycol and/or 1,4-butane diol, and mixturesof these polyalkylene terephthalates. Preferred polyalkyleneterephthalate mixtures contain 1 to 50% by weight of polyethyleneterephthalate and 99 to 50 wt % of polybutylene terephthalate.Particularly preferred mixtures contain 1 to 30 wt % of polyethyleneterephthalate and 99 to 70% by weight of polybutylene terephthalate.

The polyalkylene terephthalates preferably used generally have anintrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.3 dl/g andmore preferably 0.55 to 1.2 dl/g, as measured inphenol/o-dichlorobenzene (1:1 parts by weight) at 25° C. using anUbbelohde viscosimeter. Polyethylene terephthalate and polybutyleneterephthalate of these intrinsic viscosity ranges, and mixtures thereof,are most preferred. As is well known, polyethylene terephthalateengineering resin producers compound their products from either virginPET (typically 0.55-0.70 IV) or reclaimed PET from industrial scrap,polyester film scrap, bottles and, rarely polyester fiber scrap.

Additional thermoplastic polyesters which may be utilized in thepractice of this invention include, for example, polyetheresters,polyester-polycarbonate blends or alloys, polyester-ABS blends oralloys, polyester-MBS blends or alloys, and impact-modifiedthermoplastic polyesters.

Polyalkylene terephthalates may be produced by known methods. See, forexample, Encyclopedia of Polymer Science and Technology, Vol. 11, pages62-128, John Wiley & Sons, Inc., copyright 1969; and Kirk-Othmer,Encyclopedia of Chemical Technology, 4th Ed., Vol. 19, pages 609-653,John Wiley & Sons, Inc., copyright 1996.

Another group of preferred thermoplastic polymers which can beeffectively flame retarded by use of the pellets of this invention arepolyamides, which are sometimes referred to as nylon polymers. Suchpolyamide substrate polymer can be any amorphous and/or partlycrystalline, predominately aliphatic/cycloaliphatic or partiallyaromatic thermoplastic polyamide. Typically such materials are producedby polycondensation and/or polymerization processes from diamines whichare predominately or entirely aliphatic or cycloaliphatic in structure,or which are partially or entirely aromatic in structure, and carboxylicacids or lactams which are predominantly or entirely aliphatic orcycloaliphatic in structure, or which are partially or entirely aromaticin structure. Typical amines used in forming polyamides include suchdiamines as hexamethylenediamine, tetramethylenediamine, 2,2,4- and2,4,4-trimethyl-hexamethylenediamine, diaminodicyclohexylmethane(isomers), diaminodicyclohexylpropane (isomers) and isophoronediamine(isomers), and xylylenediamine. Also used as source materials areaminocarboxylic acids such as ε-aminocaproic acid, or ω-aminocarboxylicacids such as ω-aminolauric acid and ω-aminoundecanoic acid. Typically,the carboxylic acid used are aliphatic or mixed aliphatic-aromaticdicarboxylic acids having less than 50% by weight aromatic constituentssuch as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaicacid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid,cyclohexanedicarboxylic acid, hexahydroterephthalic acid, isophthalicacid and terephthalic acid.

Copolyamides from the majority of the known monomers can also be used.

Illustrative polyamides which may be used in the practice of thisinvention are such polyamides as nylon 6, nylon 6,6, nylon 6,9, nylon6,10, nylon 6,12, nylon 11, nylon 12, nylon 12,12, nylon 6/6,6copolymer, and high temperature nylons such as nylon 4,6, and partiallyaromatic nylons (e.g., Ixef polyarylamide PA MXD6 from Solvay, Zytel HTNfrom DuPont, and Amodel polyarylamide from Solvay). Other polyamideswhich may be used include Arlen modified polyamide 6T from MitsuiChemicals, Inc., Genestar PA9T polyamide resin from Kuraray Company,Stanyl polyamide 46 from DSM, Vydyne polyamide 6/66 copolymers fromMonsanto, polyamide 612 (Vestamid D from Creanova), and similarpolyamides. Of the various nylon polymers, nylon 6 and nylon 6,6 are thepreferred substrate polymers.

This invention is also applicable to thermoplastic blends or alloys ofone or more polyamides such as, for example, polyamide-polyolefin blendsor alloys, polyamide-ionomer blends or alloys, polyamide-ABS blends oralloys, polyamide-EPDM blends or alloys, polyamide-polyphenylene oxideblends or alloys, or impact-modified polyamides.

Methods for producing polyamide polymers are known and described in theliterature. See, for example, Encyclopedia of Polymer Science andTechnology, Vol. 10, pages 460-482, John Wiley & Sons, Inc., copyright1969; and Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed.,Vol. 19, pages 559-584, John Wiley & Sons, Inc., copyright 1996.

The following example illustrates the practice and advantages of oneembodiment this invention. This example is not intended to placelimitations upon the generic scope of this invention.

EXAMPLE

The devolatilization extruder used in this operation was a Werner &Pfleiderer ZSK-30 30 mm co-rotating twinscrew extruder. The machine hada nine-barrel configuration with an L/D ratio of 27/1. A vent waslocated on barrel 4, and a vent for application of a 30-inch vacuum onbarrel 8 was provided. A vacuum knockdown trap was provided to condensevolatiles exiting from the vent in barrel 4. The machine was operatedwith the following temperature profile: Feed throat with cooling waterON, Zone 1 at 140° C., Zone 2 at 180° C., Zone 3 at 220° C., Zone 4 at240° C. The die at the outlet was held at 230° C. The screw designprovided a gentle kneading block section in barrels 5 and 6. Operatingconditions were 125 rpm and 30% torque, with a melt temperature of 243°C. and a feed rate of an 83% solution of brominated anionic polystyrene(formed from SAYTEX® HP 3010, Albemarle Corporation) inbromochloromethane (BCM) of 8 kg/hr. Two strands were extruded onto a5-foot long takeoff belt conveyor, and gravity fed to a open drum at theend of the belt. Samples were taken from the open drum. Because of alimited material quantity of brominated anionic polystyrene availablefor this operation, the machine was operated for about 8-10 minutes. Thematerial ran smoothly during the operation. About 20-30 mL of BCMsolvent was condensed in the vacuum knockdown trap. Dry ice andisopropyl alcohol were used to cool the vacuum trap, and this wasadequate to condense the BCM even at the 30-inch Hg vacuum used. Thedevolatilized pellets of unadulterated brominated anionic polystyreneproduced had a nice appearance and had sufficient hardness to be placedinto several storage containers, two of which were transported withoutnoticeable pellet breakage.

The overall system utilized in the Example is schematically depicted inFIGS. 2 and 3. In such system, the following equipment was used:

a) The devolatilization extruder system 11 equipped and fitted, all asdescribed in the Example.

b) Die 18 was a 2-hole die with holes of 4 mm diameter.

c) Conveyor belt 20 was a Scheer-Bay conveyor having a length of 14 feet(ca. 4.3 meters), a width of 15 inches (ca. 38.1 cm), and 3-inch (ca.7.6-centimeter) diameter rollers. The mesh belt was upwardly inclined atan angle of about 12°.

d) Classifier 30 was a Witte model no 200 Classifier.

The vertical distance between the drop from the end of belt 20 to thetop of classifier 30 was about 24 inches (ca. 61 cm), and the verticaldistance between the end of transfer device 40 and the bottom ofcontainer 50 when empty was about 60 inches (ca. 152 cm). The conveyortraveled at a rate of 150 to 175 ft/min (ca. 45.7 to ca. 53.3meters/minute. The water mist was fed at a rate of about one gallon perminute (ca. 3.79 liters/minute). The air knives were operated at apressure of 10-25 psig and were disposed at about 5 inches (ca. 12.7 cm)above the surface of the conveyor belt. The vacuum applied beneath theconveyor belt was at about 2200 cubic feet per minute (ca. 62.3 cubicmeters per minute) and the vacuum was applied directly to the proximatesurface of the conveyor belt by two vacuum applicators disposedtransverse to the belt with the mouth of each applicator having an areaof 45 square inches (ca. 114.3 square centimeters).

To illustrate the improved strength properties achievable in pellets ofthis invention, there are shown in Table 2 crush strength data ofpellets produced by devolatilization extrusion of a 60 wt % solutionmade from brominated anionic polystyrene powder SAYTEX® HP 3010,Albemarle Corporation) dissolved in bromochloromethane solvent (Pelletsof This Invention) and of pellets produced not by devolatilizationextrusion of the solution, but instead by extrusion of brominatedanionic polystyrene powder (SAYTEX® HP 3010, Albemarle Corporation) asdescribed in commonly-owned published PCT patent application WO2005/118245 (Pellets Not of This Invention), pellets which are of goodquality.

TABLE 2 Pellets of This Invention Pellets Not of This Invention Length,Peak Load, Energy to Length, Peak Load, Energy to Sample inch lbs.Crush, lbs/in. Sample inch lbs. Crush, lbs/in. 1 0.190 4.44 23.37 10.143 5.06 35.38 2 0.257 6.40 24.90 2 0.206 5.44 26.41 3 0.182 7.7942.80 3 0.194 2.63 13.56 4 0.304 8.68 28.55 4 0.185 5.93 32.05 5 0.3238.28 25.63 5 0.229 14.37 62.75 6 0.323 5.51 17.06 6 0.210 5.84 27.81 70.280 9.74 34.79 7 0.178 6.73 37.81 8 0.153 10.02 65.49 8 0.191 4.3222.62 9 0.258 9.80 37.98 9 0.273 4.91 17.99 10 0.254 8.58 33.78 10 0.2954.45 15.08 11 0.285 9.54 33.47 11 0.354 4.34 12.26 12 0.386 10.75 27.8512 0.329 3.47 10.55 13 0.473 12.25 25.90 13 0.415 5.34 12.87 Average0.282 8.60 32.43 Average 0.246 5.60 25.16 Std. 0.086 2.16 12.04 Std.0.081 2.84 14.60 Deviation Deviation

Components referred to by chemical name or formula anywhere in thespecification or claims hereof, whether referred to in the singular orplural, are identified as they exist prior to coming into contact withanother substance referred to by chemical name or chemical type (e.g.,another component, a solvent, or etc.). It matters not what preliminarychemical changes, transformations and/or reactions, if any, take placein the resulting mixture or solution as such changes, transformations,and/or reactions are the natural result of bringing the specifiedcomponents together under the conditions called for pursuant to thisdisclosure. Thus the components are identified as ingredients to bebrought together in connection with performing a desired operation or informing a desired composition. Also, even though the claims hereinaftermay refer to substances, components and/or ingredients in the presenttense (“comprises”, “is”, etc.), the reference is to the substance,component or ingredient as it existed at the time just before it wasfirst contacted, blended or mixed with one or more other substances,components and/or ingredients in accordance with the present disclosure.The fact that a substance, component or ingredient may have lost itsoriginal identity through a chemical reaction or transformation duringthe course of contacting, blending or mixing operations, if conducted inaccordance with this disclosure and with ordinary skill of a chemist, isthus of no practical concern.

Each and every patent or other publication or published documentreferred to in any portion of this specification is incorporated in totointo this disclosure by reference, as if fully set forth herein.

Except as may be expressly otherwise indicated, the article “a” or “an”if and as used herein is not intended to limit, and should not beconstrued as limiting, a claim to a single element to which the articlerefers. Rather, the article “a” or “an” if and as used herein isintended to cover one or more such elements, unless the text expresslyindicates otherwise.

This invention is susceptible to considerable variation in its practice.Therefore the foregoing description is not intended to limit, and shouldnot be construed as limiting, the invention to the particularexemplifications presented hereinabove.

1. A process for the preparation of a brominated styrenic polymer in theform of a melt or polymer flow, which process comprises: brominating astyrenic polymer under superatmospheric pressure in a vaporizablesolvent and in the presence of a Lewis acid bromination catalyst, and ina closed reaction system in which substantially all of the hydrogenhalide coproduct is retained in the reaction mixture; quenching thecatalyst to thereby form (i) an organic phase containing dissolvedbrominated styrenic polymer and (ii) an aqueous phase containinghydrogen halide; separating phases (i) and (ii) from each other, and ifphase (i) has a viscosity less than extrudable viscosity, concentratingorganic phase of (i) to form an admixture of extrudable viscosity;continuously introducing organic phase of (i) or admixture of extrudableviscosity into the liquids inlet portion of an operatingdevolatilization extruder having a liquids inlet portion and a polymermelt or polymer flow outlet portion and at least two sections that canbe operated (a) at temperatures that differ from each other, and (b)under pressures that differ from each other, one of the at least twosections being disposed upstream from the other of the at least twosections, the devolatilization extruder having vapor collectingapparatus adapted to collect volatiles formed in these at least twosections; and operating said section disposed downstream at highertemperature and lower pressure conditions than the temperature andpressure conditions of said section disposed upstream, so that (a) aflowable polymer melt or polymer flow of said polymer is formed withinthe devolatilization extruder and released from the at least one polymermelt or polymer flow outlet, and (b) volatiles composed predominately ofthe solvent released from the polymer in said at least two sections arecollected by said vapor collecting apparatus, the polymer melt orpolymer flow of such brominated styrenic polymer leaving from the outletportion of the devolatilization extruder during steady-state operationof the devolatilization extruder containing an average of less thanabout 10,000 ppm (wt/wt) of the organic solvent used in the process. 2.A process as in claim 1 wherein the styrenic polymer that is to bebrominated in the process is at least one anionic styrenic polymerhaving a GPC weight average molecular weight (M_(w)) in the range ofabout 2000 to about 200,000 and a GPC polydispersity in the range of 1to about 2, wherein the brominated anionic styrenic polymer formed insaid process has a bromine content of at least about 50 wt %.
 3. Aprocess as in claim 2 wherein said GPC weight average molecular weight(M_(w)) is in the range of about 3000 to about 10,000 and said brominecontent is at least about 60 wt %.
 4. A process as in claim 3 whereinsaid GPC weight average molecular weight (M_(w)) is in the range ofabout 3000 to about 7000 and said bromine content is at least about 67wt %.
 5. A process as in claim 1 wherein the styrenic polymer that isbrominated in the process is at least one free-radically producedstyrenic polymer having a GPC weight average molecular weight (M_(w)) inthe range of about 30,000 to about 500,000 and a GPC polydispersity inthe range of 1 to about 10, and wherein the brominated styrenic polymerformed in said process has a bromine content of at least about 50 wt %.6. A process as in claim 5 wherein said GPC weight average molecularweight (M_(w)) is in the range of about 50,000 to about 300,000 and saidbromine content is at least about 60 wt %.
 7. A process as in claim 6wherein said GPC weight average molecular weight (M_(w)) is in the rangeof about 150,000 to about 250,000 and said bromine content is at leastabout 67 wt %.